Weatherability of flame retardant polyolefin

ABSTRACT

Stabilized thermoplastic polymer, especially polyolefin compositions comprising a flame retardant selected from b1) melamin based flame retardants, or one of the compounds b2) bis-(hexachlorocyclopentadieno) cyclooctane, b3) tris-(2,3-dibromopropyl)-isocyanurate, b4) ethylene-bis-tetrabromophthalimide; b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecan, b6) ethane-1,2-bis(pentabromophenyl); and c) a sterically hindered amine light stabilizer of the hydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class and optional further components combine optimum outdoor weathering stability and good flame retardant properties.

The instant invention pertains to a thermoplastic organic polymer,especially a polyolefin such as thermoplastic polyolefin (TPO),stabilized against the deleterious effects of light, oxygen and heat andcontaining a certain flame retardant, which contains a stericallyhindered amine of the hydrocarbyloxyamine or hydroxyhydrocarbyloxyamineclass and optionally further stabilizers, to the use of these flameretardants and sterically hindered amines for imparting both lightstabilization and flame retardant properties, and to a correspondingprocess for improving light stability and flame retardancy of athermoplastic organic polymer.

U.S. Pat. No. 5,393,812 does describe polyolefin compositions which aremade flame retardant by addition of a halogenated hydrocarbyl phosphateor phosphonate ester flame retardant, and stabilized against weatheringwith a alkoxyamine functional hindered amine. EP-A-792911 proposes theuse of a alkoxyamine functional hindered amine for improving the flameretardant properties of a polyolefin. The activity of alkoxyaminefunctional hindered amines alone as a flame retardant is disclosed in WO99/00450.

There is still need to improve flame retardant polymer compositions inorder to obtain good stability against weathering.

Now it has been found that optimum stabilization against UV light andweathering and good flame retardant properties, especially for outdoorapplications, can be combined in a thermoplastic polymer, especially apolyolefin, polyolefin copolymer or blend thereof such as impactmodified polyolefin or thermoplastic polyolefin (TPO), when certainhindered amine stabilizers are used in combination with a specific flameretardant. Thus, present invention pertains to the use of a combinationof a flame retardant selected from

-   -   b1) melamin based flame retardants and/or ammonium        polyphosphate,    -   b2) bis-(hexachlorocyclopentadieno) cyclooctane,    -   b3) tris-(2,3-dibromopropyl)-isocyanurate,    -   b4) ethylene-bis-tetrabromophthalimide,    -   b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecan,    -   b6) ethane-1,2-bis(pentabromophenyl); and    -   c) a sterically hindered amine light stabilizer of the        hydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class for        imparting both weathering stability and flame retardancy to a        thermoplastic polymer (a),        provided that the flame retardant is not (b4) if the sterically        hindered amine is of the hydroxyhydrocarbyloxy class.

DETAILED DISCLOSURE

The sterically hindered amine light stabilizer of thehydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class of component (c)is characterized by its substituent E₁-O— on the amino nitrogen atom(see formula below), wherein E₁ is preferably C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl or C₇-C₁₅aralkyl in the sterically hindered amine ofthe hydrocarbyloxyamine class; and E₁ is preferably C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl or C₇-C₁₅aralkyl each of which is substituted in thealiphatic part by 1-3 OH groups in the sterically hindered amine of thehydroxyhydrocarbyloxyamine class. The latter type of compound,containing a reactive OH group, may also be used in the form of itsreaction product.

The sterically hindered amine light stabilizer of thehydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class of component cusually is a compound containing a group of the formula

where G₁ and G₂ are independently alkyl of 1 to 4 carbon atoms or aretogether pentamethylene, and

-   -   E₁ is C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl or C₇-C₁₅aralkyl; or E₁ is        C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl or C₇-C₁₅aralkyl each of which is        substituted in the aliphatic part by 1-3 OH groups; or is a        reaction product thereof. Preferred is a cyclic sterically        hindered amine conforming to the formula        wherein    -   G₁, G₂ and E₁ are as defined above;    -   T is a divalent organic radical required to complete formula I        to form, together with the hindered amine nitrogen atom and the        two quaternary carbon atoms substituted by G₁ and G₂, a five- or        six-membered aliphatic ring structure, especially a piperidine        ring;    -   or is an oligomeric or polymeric hindered amine molecule made        from the reaction of a dialkyl ester or isocyanate with a        compound of the formula (I) wherein E₁ contains 1 OH group and T        is —CH₂—CH(OH)—CH₂—;    -   or is a simple diester or urethane derivative of a compound of        the formula (I) wherein E₁ contains 1 OH group and T is        —CH₂—CH(OH)—CH₂—.

In general, effective stabilizing amounts of a compound of component cused are from 0.01 to 10%, preferably from 0.05 to 5% by weight,especially from 0.1 to 2% by weight, based on the polymer component (a),of the stabilizer of component (c).

Sterically hindered amines of present component (c) are largely known aslight stabilizers (U.S. Pat. No. 5,004,770; U.S. Pat. No. 5,096,950;U.S. Pat. No. 5,204,473; U.S. Pat. No. 5,096,950; U.S. Pat. No.5,300,544; U.S. Pat. No. 6,117,995; U.S. Pat. No. 6,271,377).

Flame retardants of component (b) are commercial compounds. Mostpreferred is tris-(2,3-dibromopropyl)-isocyanurate (b3).

Halogen-free flame retardants b1 are usually employed in an amount from1 to about 50% by weight of the polymer (a), preferably in an amountfrom 5 to 50% by weight of the polymer (a). The ratio b1:c is mostpreferably in the range from 20:1 to 250:1.

Halogenated flame retardants b2, b3, b4, b5 and/or b6 are usuallyemployed in a total amount from 0.5 to 40% by weight of the polymer (a);more preferably 3 to 40%, most preferably 5 to 35% by weight of polymer(a).

Most preferred amounts of flame retardants (b) in the compositions ofpresent invention are for

-   -   b1) the melamin based flame retardant and/or ammonium        polyphosphate 20-50%;    -   b2) bis-(hexachlorocyclopentadieno) cyclooctane 5-20%;    -   b3) tris-(2,3-dibromopropyl)-isocyanurate 2-10%;    -   b4) ethylene-bis-tetrabromophthalimide 10-40%;    -   b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecan 2-20%;    -   b6) ethane-1,2-bis(pentabromophenyl) 2-20%;    -   each amount denotes percent by weight, based on the weight of        the polymer (a).

Also of importance in the context of present invention is the use of theflame retardant tris(3-bromo-2,2-(bromomethyl)propyl) phosphate (b7; seebelow), which is most preferably employed in an amount of 2-20,especially 2-10, percent by weight, based on the weight of the polymer(a).

The ratio of halogenated flame retardants b2, b3, b4, b5, b6 or b7:c ismost preferably in the range from 5:1 to 100:1.

Advantageously, halogenated flame retardants such as b2, b3, b4, b5, b6and/or b7 may be used in combination with an appropriate synergist suchas an antimon compound (often Sb₂O₃), which is commonly added in anamount of 0.5 to 20% by weight of the polymer (a).

Component a is frequently selected from the following thermoplasticpolymers:

1. Polymers of monoolefins and diolefins, for example polypropylene(PP), polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbomene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), highdensity and high molecular weight polyethylene (HDPE-HMW), high densityand ultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylenefisobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM.

In the following, the term polyolefin will be used for pure polyolefinhomopolymers as well as copolymers and blends thereof.

Preferably, the polyolefin or thermoplastic olefin or polyolefin (TPO)is the only organic polymer present in these compositions; mainly it ispolyethylene (PE) or polypropylene (PP), especially LDPE, LLDPE or PP,or copolymers of PP and PE.

Especially preferred as component (a) are polymers known asthermoplastic (poly)olefines (TPO), e.g. polypropylene or polyethylenecontaining an impact modifyer or elastomer component such as EPR etc.,or heterophasic copolymers (see e.g. W. Neissl et al., Kunststoffe 83,No. 8, 1993).

Examples of polymer compositions in which the instant compounds areeffective include flame retardant polyolefins where acidic residues fromthe decomposition of the halogenated flame retardants deactivatehindered amines not having the N—OR group, roofing membranes, greenhousefilms and agricultural mulch films where acidic residues from pesticidesinterfere with the activity of “normal” hindered amine stabilizers, andin thermoplastic polyolefins where pigment interactions with basichindered amine stabilizers interfere with painting the substratesurfaces.

Preferably, the compound of present component c is a cyclic stericallyhindered amine containing a group of formula (II) and/or (III)

in which G is hydrogen or methyl, and G₁ and G₂, independently of oneanother, are hydrogen, methyl or together are a substituent ═O.

Examples of sterically hindered amines of present component c aredescribed below under classes (a′) to (m′).

(a′) A compound of the formula (1a)

in which n₁ is a number from 1 to 4, G and G₁, independently of oneanother, are hydrogen or methyl,

-   -   G₁₁ is O, hydroxyl, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy,        C₇-C₁₅phenylalkoxy; or G., is C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy or        C₇-C₁₅phenylalkoxy each of which is substituted in the aliphatic        part by 1-3 OH groups; G₁₁ preferably being C₁-C₁₂alkoxy or        cyclohexyloxy or C₂-C₈hydroxyalkoxy, especially octyloxy,        cyclohexyloxy or 2-hydroxy-2-methylpropoxy, and G₁₂, if n₁ is 1,        is hydrogen, C₁-C₁₈alkyl which is uninterrupted or interrupted        by one or more oxygen atoms, COO and/or CONH groups, or is        cyanoethyl, benzoyl, glycidyl, a monovalent radical of an        aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic        carboxylic acid, carbamic acid or phosphorus-containing acid or        a monovalent silyl radical, preferably a radical of an aliphatic        carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic        carboxylic acid having 7 to 15 carbon atoms, or an        α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of        an aromatic carboxylic acid having 7 to 15 carbon atoms, where        each carboxylic acid can be substituted in the aliphatic,        cycloaliphatic or aromatic moiety by 1 to 3-COOZ₁₂ groups, in        which Z₁₂ is H, C₁-C₂₀alkyl, C₃-C₁₂alkenyl, C₅-C₇cycloalkyl,        phenyl or benzyl,    -   G₁₂, if n₁ is 2, is C₂-C₁₂alkylene, C₄-C₁₂alkenylene, xylylene,        a divalent radical of an aliphatic, cycloaliphatic, araliphatic        or aromatic dicarboxylic acid, dicarbamic acid or        phosphorus-containing acid or a divalent silyl radical,        preferably a radical of an aliphatic dicarboxylic acid having 2        to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic        acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic        or aromatic dicarbamic acid having 8-14 carbon atoms, where each        dicarboxylic acid may be substituted in the aliphatic,        cycloaliphatic or aromatic moiety by one or two —COOZ₁₂ groups,    -   G₁₂, if n₁ is 3, is a trivalent radical of an aliphatic,        cycloaliphatic or aromatic tricarboxylic acid, which may be        substituted in the aliphatic, cycloaliphatic or aromatic moiety        by —COOZ₁₂, of an aromatic tricarbamic acid or of a        phosphorus-containing acid, or is a trivalent silyl radical,        preferred radicals including triacyl radicals of nitrilo        triacetic acid of benzene tricarboxylic acid,    -   and G₁₂, if n₁ is 4, is a tetravalent radical of an aliphatic,        cycloaliphatic or aromatic tetracarboxylic acid.

The carboxylic acid radicals mentioned above are in each case taken tomean radicals of the formula (—CO)_(x)R, where x is as defined above forn₁, and the meaning of R arises from the definition given above.

Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-hexadecyl or n-octadecyl.

C₁-C₁₈alkoxy G₁₁ is, for example, methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy,decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.C₆-C₁₂alkoxy, in particular heptoxy and octoxy, is preferred.

C₅-C₁₂cycloalkoxy G₁₁ is, for example, cyclopentoxy, cyclohexoxy,cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.C₅-C₈cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, ispreferred.

C₇-C₉phenylalkoxy is, for example, benzyloxy. G₁₁ as C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy or C₇-C₁₅phenylalkoxy substituted in the aliphaticpart by 1-3 OH groups is a radical formed by abstraction of ancarbon-bonded hydrogen atom preferably from 2-methyl-2-propanol(tert.-butanol), 2-propanol, 2,2-dimethyl-1-propanol,2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol,2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allylalcohol, phenethyl alcohol or 1-phenyl-1-ethanol; 1,2-ethanediol,1,2-propanedial, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol,1,3-cyclohexanediol or 1,4-cyclohexanediol; glycerol,1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol.

More preferably, G₁₁ is are formed from 2-methyl-2-propanol orcyclohexanol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol. Mostpreferred hydroxy substituted G₁₁ is 2-hydroxy-2-methylpropoxy.

Examples of several G₁₂ radicals are given below.

If G₁₂ is a monovalent radical of a carboxylic acid, it is, for example,an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl orO-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

If G₁₂ is a monovalent silyl radical, it is, for example, a radical ofthe formula —(C_(j)H_(2j))—Si(Z′)₂Z″, in which j is an integer in therange from 2 to 5, and Z′ and Z″, independently of one another, areC₁-C₄alkyl or C₁-C₄alkoxy.

If G₁₂ is a divalent radical of a dicarboxylic acid, it is, for example,a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl,itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl,butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl orbicycloheptenedicarbonyl radical or a group of the formula

If G₁₂ is a trivalent radical of a tricarboxylic acid, it is, forexample, a trimellitoyl, citryl or nitrilotriacetyl radical.

If G₁₂ is a tetravalent radical of a tetracarboxylic acid, it is, forexample, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acidor of pyromellitic acid.

If G₁₂ is a divalent radical of a dicarbamic acid, it is, for example,hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

Preference is given to compounds of the formula (1a) in which G and G₁are hydrogen, G₁₁ is hydrogen or methyl, n, is 2 and G₁₂ is the diacylradical of an aliphatic dicarboxylic acid having 4-12 carbon atoms.

(b′) A compound of the formula (1b)

in which n₂ is the number 1, 2 or 3, and G, G₁ and G₁₁ are as definedunder (a′), G₁₃ is hydrogen, C₁-C₁₂alkyl, C₂-C₅hydroxyalkyl,C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₁-C₁₈alkanoyl, C₃-C₅alkenoyl, benzoyl ora group of the formula

and G₁₄, if n₂ is 1, is hydrogen, C₁-C₁₈alkyl, C₃-C₈alkenyl,C₅-C₇cycloalkyl, C₁-C₄alkyl which is substituted by a hydroxyl, cyano,alkoxycarbonyl or carbamide group or group of the formula —CONH-Z, orG₁₄ is glycidyl, a group of the formula —CH₂—CH(OH)-Z or of the formula—CONH-Z, in which Z is hydrogen, methyl or phenyl or CH₂—OZ₁₄ with Z₁₄being hydrogen or C₁-C₁₈alkyl;

-   -   G₁₄, if n₂ is 2, is C₂-C₁₂alkylene, C₆-C₁₂arylene, xylylene, a        —CH₂—CH(OH)—CH₂ group or a —CH₂—CH(OH)—CH₂—O-D-O— group, in        which D is C₂-C₁₀alkylene, C₆-C₁₅arylene, C₆-C₁₂cycloalkylene,        or, provided that G₁₃ is not alkanoyl, alkenoyl or benzoyl, G₁₄        can alternatively be 1-oxo-C₂-C₁₂alkylene, a divalent radical of        an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or        dicarbamic acid or alternatively the group —CO—, G₁₄, if n₂ is        3, is a group        or, if n₂ is 1, G₁₃ and G₁₄ together can be the divalent radical        of an aliphatic, cycloaliphatic or aromatic 1,2- or        1,3-dicarboxylic acid.

Some examples for the radicals G₁₃, G₁₄ and D are given below.

Any alkyl substituents are as defined above for (a′).

Any C₅-C₇Cycloalkyl substituents are, in particular, cyclohexyl.

C₇-C₈aralkyl G₁₃ is, in particular, phenylethyl or especially benzyl.

C₂-C₅hydroxyalkyl G₁₃ is, in particular, 2-hydroxyethyl or2-hydroxypropyl.

C₁-C₁₈alkanoyl G₁₃ is, for example, formyl, acetyl, propionyl, butyryl,octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl,and C₃-C₅alkenoyl G₁₃ is, in particular, acryloyl.

C₂-C₈alkenyl G₁₄ is, for example, allyl, methallyl, 2-butenyl,2-pentenyl, 2-hexenyl or 2-octenyl.

G₁₄ as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substitutedC₁-C₄alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl,2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl,2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

Any C₂-C₁₂alkylene radicals are, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

Any C₆-C₁₅arylene substituents are, for example, o-, m- or p-phenylene,1,4-naphthylene or 4,4′-diphenylene.

C₆-C₁₂cycloalkylene is, in particular, cyclohexylene.

G₁₄ as 1-oxo-C₂-C₁₂alkylene is preferably a group

(c′) A compound of the formula (1c)

in which n₃ is the number 1 or 2, G, G₁ and G₁₁ are as defined under(a′), and G₁₅ and G′₁₅ if n₃ is 1, are independently C₁-C₁₂ alkyl,C₂-C₁₂ alkenyl, C₇-C₁₂ aralkyl, or G₁₅ is also hydrogen, or G₁₅ and G′₁₅together are C₂-C₈alkylene, C₅-C₁₅alkenylene, C₂-C₈hydroxyalkylene orC₄-C₂₂acyloxyalkylene, and if n₃ is 2, G₁₅ and G′₁₅ together are the(—CH₂)₂C(CH₂—)₂ group.

C₂-C₈alkylene or C₂-C₈hydroxyalkylene G₁₅ and G′₁₅ is, for example,ethylene, 1-methylethylene propylene, 2-ethylpropylene or2-ethyl-2-hydroxymethylpropylene.

-   -   C₄-C₂₂acyloxyalkylene G₁₅ and G′₅ is, for example,        2-ethyl-2-acetoxymethylpropylene.

(d′) A compound of the formula (1d-1), (1d-2) or (1d-3),

in which n₄ is the number 1 or 2, G, G₁ and G₁₁ are as defined under(a′), G₁₆ is hydrogen, C₁-C₁₂alkyl, allyl, benzyl, glycidyl orC₂-C₆alkoxyalkyl, and G₁₇, if n₄ is 1, is hydrogen, C₁-C₁₂alkyl,C₃-C₅alkenyl, C₇-C₉aralkyl, C₅-C₇cycloalkyl, C₂-C₄hydroxyalkyl,C₂-C₆alkoxyalkyl, C₆-C₁₀aryl, glycidyl or a group of the formula—(CH₂)_(p)—COO-Q or —(CH₂)_(p)—O—CO-Q, in which p is 1 or 2, and Q isC₁-C₄alkyl or phenyl, and G₁₇, if n₄ is 2, is C₂-C₁₂alkylene,C₄-C₁₂alkenylene, C₆-C₁₂arylene, a group of the formula—CH₂—CH(OH)—CH₂—O-D′-O—CH₂—CH(OH)—CH₂—, in which D′ is C₂-C₁₀alkylene,C₆-C₁₅arylene or C₆-C₁₂cycloalkylene, or a group of the formula—CH₂CH(OD″)CH₂—(OCH₂—CH(OD″)CH₂)₂—, in which D″ is hydrogen,C₁-C₁₈alkyl, allyl, benzyl, C₂-C₁₂alkanoyl or benzoyl, T₁ and T_(2,)independently of one another, are hydrogen, C₁-C₁₈alkyl or unsubstitutedor halogen- or C₁-C₄alkyl-substituted C₆-C₁₀aryl or C₇-C₉aralkyl, or

-   -   T₁ and T₂ together with the carbon atom bonding them form a        C₅-C₁₄cycloalkane ring.

Any C₁-C₁₂alkyl substituents are, for example, methyl, ethyl, n-propyl,n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl,n-decyl, n-undecyl or n-dodecyl.

Any C₁-C₁₈alkyl substituents can be, for example, the abovementionedgroups and in addition, for example, n-tridecyl, n-tetradecyl,n-hexadecyl or n-octadecyl.

Any C₂-C₆alkoxyalkyl substituents are, for example, methoxymethyl,ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl,ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl orpropoxypropyl.

C₃-C₅alkenyl G₁₇ is, for example, 1-propenyl, allyl, methallyl,2-butenyl or 2-pentenyl.

C₇-C₉aralkyl G₁₇, T₁ and T₂ are, in particular, phenethyl or especiallybenzyl. If T₁ and T₂ together with the carbon atom form a cycloalkanering, this can be, for example, a cyclopentane, cyclohexane, cyclooctaneor cyclododecane ring.

C₂-C₄hydroxyalkyl G₁₇ is, for example, 2-hydroxyethyl, 2-hydroxypropyl,2-hydroxybutyl or 4-hydroxybutyl.

C₆-C₁₀aryl G₁₇, T₁ and T₂ are, in particular, phenyl or α- orβ-naphthyl, which are unsubstituted or substituted by halogen orC₁-C₄alkyl.

C₂-C₁₂alkylene G₁₇ is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

C₄-C₁₂alkenylene G₁₇ is, in particular, 2-butenylene, 2-pentenylene or3-hexenylene.

C₆-C₁₂arylene G₁₇ is, for example, o-, m- or p-phenylene,1,4-naphthylene or 4,4′-diphenylene.

C₂-C₁₂alkanoyl D″ is, for example, propionyl, butyryl, octanoyl,dodecanoyl, but preferably acetyl.

C₂-C₁₀alkylene, C₆-C₁₅arylene or C₆-C₁₂cycloalkylene D′ have, forexample, one of the definitions given for D under (b′).

(e′) A compound of the formula (1e)

in which n₅ is the number 1 or 2, and G₁₈ is a group of the formula

in which G and G₁₁ are as defined under (a′), and G₁ and G₂ arehydrogen, methyl or, together, are a substituent ═O,

-   -   E is —O— or —ND′″-,    -   A is C₂-C₆alkylene or —(CH₂)₃—O— and    -   x₁ is the number 0 or 1,    -   D′″ is hydrogen, C₁-C₁₂alkyl, C₂-C₁₂alkylene-N(D^(V))₂,        C₂-C₅hydroxyalkyl or C₅-C7cycloalkyl, where D^(V),        independently, is hydrogen or butyl,    -   G₁₉ is identical to G₁₈ or is one of the groups —N(G₂₁)(G₂₂),        —OG₂₃, —N(H)(CH₂OG₂₃) or —N(CH₂OG₂₃)₂,    -   G₂₀, if n₅=1, is identical to G₁₈ or G₁₉ and, if n₅=2, is an        -E-D^(IV)-E- group, in which D^(IV) is C₂-C₈alkylene or        C₂-C₈alkylene which is interrupted by 1 or 2-NG₂₁- groups,    -   G₂₁ is hydrogen, C₁-C₁₂alkyl, cyclohexyl, benzyl or        C₁-C₄-hydroxyalkyl or a group of the formula    -   G₂₂ is C₁-C₁₂alkyl, cyclohexyl, benzyl or C₁-C₄hydroxyalkyl, and    -   G₂₃ is hydrogen, C₁-C₁₂alkyl or phenyl, or G₂₁ and G₂₂ together        are C₄-C₅alkylene or C₄-C₅oxaalkylene, for example        —CH₂CH₂—O—CH₂CH₂—, or a group of the formula        —CH₂CH₂—N(G₁₁)-CH₂CH₂—.

Some examples of the several variables in the formula (Ie) are givenbelow.

Any C₁-C₁₂alkyl substituents are, for example, methyl, ethyl; n-propyl,n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl,n-decyl, n-undecyl or n-dodecyl.

Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Any C₅-C₇cycloalkyl substituents are, for example, cyclopentyl,cyclohexyl or cycloheptyl. Cyclohexyl is preferred.

C₂-C₆alkylene A is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene or hexamethylene.

If G₂₁ and G₂₂ together are C₄-C₅alkylene or oxaalkylene, they are, forexample, tetramethylene, pentamethylene or 3-oxapentamethylene.

(f′) A compound of the formula (1f)

wherein G₁₁ is as defined under (a′).

(g′) Oligomeric or polymeric compounds whose recurring structural unitcontains a 2,2,6,6-tetraalkylpiperidinyl radical, in particularpolyesters, polyethers, polyamides, polyamines, polyurethanes,polyureas, polyaminotriazines, poly(meth)acrylates,poly(meth)acrylamides and copolymers thereof which contain suchradicals.

Examples of 2,2,6,6-polyalkylpiperidine compounds from this class arethe compounds of the following formulae. m₁ to m₁₄ is a number from 2 toabout 200, preferably 2 to 100, for example 2 to 50, 2 to 40, 3 to 40 or4 to 10.

The meanings of the end groups which saturate the free valences in theoligomeric or polymeric compounds listed below depend on the processesused for the preparation of said compounds. The end groups can also inaddition be modified after the synthesis of the compounds.

Examples for polymeric compounds are:

-   -   1) A compound of the formula (1g)        wherein G₂₄, G₂₅, G₂₆, G₂₇ and G₂₈, independently of one        another, are a direct bond or C₁-C₁₀alkylene, G₁₁ is as defined        under (a′) and m₁₇ is a number from 1 to 50.

In the compound of the formula (1g), the end group bonded to the >C═Ogroup can be, for example,

and the end group bonded to the oxygen can be, for example

-   -   2) Compound of the formula (2g)        in which the index m,₈ ranges from 1 to 15;    -   R₁₂ is C₂-C₁₂alkylene, C₄-C₁₂alkenylene, C₅-C₇cycloalkylene,        C₅-C₇cycloalkylene-di(C₁-C₄alkylene),        C₁-C₄alkylenedi(C₅-C₇Cycloalkylene), phenylenedi(C₁-C₄alkylene)        or C₄-C₁₂alkylene interrupted by 1,4-piperazinediyl, —O— or        >N—X₁ with X₁ being C₁-C₁₂acyl or (C₁-C₁₂alkoxy)carbonyl or        having one of the definitions of R₁₄ given below except        hydrogen;    -   or R₁₂ is a group of the formula (2g′) or (2g″);    -   X₂ being C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl which is unsubstituted or        substituted by 1, 2 or 3 C₁-C₄alkyl; phenyl which is        unsubstituted or substituted by 1, 2 or 3 C₁-C₄alkyl or    -   C₁-C₄alkoxy; C₇-C₉phenylalkyl which is unsubstituted or        substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; and    -   the radicals X₃ being independently of one another        C₂-C₁₂alkylene;    -   the radicals A are independently of one another —OR₁₃,        —N(R₁₄)(R₁₅) or a group of the formula (2g′″);    -   R₁₃, R₁₄ and R₁₅, which are identical or different, are        hydrogen, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl which is unsubstituted        or substituted by 1, 2 or 3 C₁-C₄alkyl; C₃-C₁₈alkenyl, phenyl        which is unsubstituted or substituted by 1, 2 or 3 C₁-C₄alkyl or        C₁-C₄alkoxy; C₇-C₉phenylalkyl which is unsubstituted or        substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl;        tetrahydrofurfuryl or C₂-C₄alkyl which is substituted in the 2,        3 or 4 position by —OH, C₁-C₈alkoxy, di(C₁-C₄alkyl)amino or a        group of the formula (2g^(IV));        with Y being —O—, —CH₂—, —CH₂CH₂— or >N—CH₃,    -   or —N(R₁₄)(R₁₅) is additionally a group of the formula        (2g^(IV));    -   X is —O— or >N—R₁₆;    -   R₁₆ is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₅-C₁₂cycloalkyl        which is unsubstituted or substituted by 1, 2 or 3 C₁-C₄alkyl;        C₇-C₉phenylalkyl which is unsubstituted or substituted on the        phenyl by 1, 2 or 3 C₁-C₄alkyl; tetrahydrofurfuryl, a group of        the formula (2g^(V)),        or C₂-C₄alkyl which is substituted in the 2, 3 or 4 position by        —OH, C₁-C₈alkoxy, di(C₁-C₄alkyl)amino or a group of the formula        (2g^(IV));    -   R₁₁ has one of the definitions given for R₁₆; and    -   the radicals B have independently of one another one of the        definitions given for A.

3) A compound of the formula (3g)

in which G₁₁ is as defined under (a′), G₂₉ and G₃₂, independently of oneanother, are a direct bond or a —N(X₁)—CO—X₂—CO—N(X₃)— group, where X₁and X₃, independently of one another, are hydrogen, C₁-C₈alkyl,C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkyl or a group of the formula

and X₂ is a direct bond or C₁-C₄alkylene, G₃₀, G₃₁, G₃₄ and G₃₅,independently of one another, are hydrogen, C₁-C₃₀alkyl,C₅-C₁₂cycloalkyl or phenyl, G₃₃ is hydrogen, C₁-C₃₀alkyl,C₅-C₁₂cycloalkyl, C₇-C₉phenylalkyl, phenyl or a group of the formula(3g), and m₁₉ is a number from 1 to 50.

In the compounds of the formula (3g), the end group bonded to the2,5-dioxopyrrolidine ring can be, for example, hydrogen, and the endgroup bonded to the —C(G₃₄)(G₃₅)- radical can be, for example,

4) A product obtainable by reacting an intermediate product, obtained byreaction of a polyamine of the formula (4g) with cyanuric chloride, witha compound of the formula (4g′)

in which m′₂₀, m″₂₀ and m′″₂₀, independently of one another, are anumber from 2 to 12, G₃₆ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl,phenyl or C₇-C₉phenylalkyl, and G₁₁ is as defined under (a′).

In general, the above reaction product can be represented for example bya compound of the following 3 formulae. It can also be in the form of amixture of these three compounds:

5) A compound of the formula (5g)

in which G₁₁ is as defined under (a′), G₃₇ is C₁-C₁₀alkyl,C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl orC₁-C₁₀alkyl-substituted phenyl, G₃₈ is C₃-C₁₀alkylene and m₂₁ is anumber from 1 to 50.

In the compounds of the formula (5g), the terminal group bonded to thesilicon atom can be, for example, (G₃₇)₃Si—O—, and the terminal groupbonded to the oxygen can be, for example, —Si(G₃₇)₃.

The compounds of the formula (5g) can also be in the form of cycliccompounds if m₂₁ is a number from 3 to 10, i.e. the free valences shownin the structural formula then form a direct bond.

6) A compound of the formula (6g)

where E is —O— or —ND′″- as defined under (e′), T₃ is ethylene or1,2-propylene, is the repeating structural unit derived from analpha-olefin copolymer with an alkyl acrylate or methacrylate;preferably a copolymer of ethylene and ethyl acrylate, and where k is 2to 100.

7) A compound of the formula (7g)

wherein m is 1 to 100;

G50 is straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbonatoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chainalkylene of 1 to 4 carbon atoms substituted by phenyl or by phenylsubstituted by one or two alkyl of 1 to 4 carbon atoms, with the provisothat in formula (7g) successive hindered amine moieties can be orientedin either a head to head or head to tail fashion;

-   -   T₄ is hydrogen or    -   T₄ is    -   G₅₅ is a straight or branched chain alkylene of 1 to 18 carbon        atoms, cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms,        phenylene or —NH-alkylene-NH— of 2 to 18 carbon atoms including        5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane and        —NH-xylylene-NH—;    -   T₅ is alkyl of 1 to 4 carbon atoms;

In the above shown oligomeric and polymeric compounds, examples of alkylare methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethyl-hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,eicosyl and docosyl;

-   -   examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl        and cyclooctyl;    -   an example of C₇-C₉phenylalkyl is benzyl; and    -   examples of alkylene are ethylene, propylene, trimethylene,        tetramethylene, pentamethylene, 2,2-dimethyltrimethylene,        hexamethylene, trimethylhexamethylene, octamethylene and        decamethylene.

(h′) A compound of the formula (1h)

in which n₆ is the number 1 or 2, G and G₁ are as defined under (a′),and G₁₄ is as defined under (b′), but G₁₄ cannot be —CONH-Z and—CH₂—CH(OH)—CH₂-O-D-O—.

(i′) A compound of the formula (1i)

wherein the radicals G₃₉, independently of one another, are a group ofthe formula (1i-1)

in which G₄₀ is C₁-C₁₂alkyl or C₅-C₁₂cycloalkyl, G₄₁ is C₂-C₁₂alkyleneand G₄₂ is as defined for G₁₁ above.

Alkyl is for example C₁-C₄alkyl, in particular methyl, ethyl, propyl orbutyl.

Cycloalkyl is preferably cyclohexyl.

Alkylene is for example ethylene, propylene, trimethylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene orhexamethylene.

Alkenyl is preferably allyl.

Phenylalkyl is preferably benzyl.

Acyl is preferably acetyl.

(j′) A compound of the formula (1j)

wherein G, G₁₁ are as defined above and

-   -   when n₇ is 1, T₇ is hydrogen, C₁-C₁₂alkyl, C₃-C₅alkenyl,        C₇-C₉aralkyl, C₅-C₇cycloalkyl, C₂-C₄hydroxyalkyl,        C₂-C₆alkoxyalkyl, C₆-C₁₀ aryl, glycidyl, a group of the formula        —(CH₂)_(t)—COO-Q or of the formula —(CH₂)_(t)—O—CO-Q wherein t        is 1 or 2, and Q is C₁-C₄alkyl or phenyl; or    -   when n₇ is 2, T₇ is C₂-C₁₂alkylene, C₆-C₁₂arylene, a group        —CH₂CH(OH)—CH₂—O—X—O—CH₂—CH(OH)—CH₂— wherein X is        C₂-C₁₀alkylene, C₆-C₁₅arylene or C₆-C₁₂cycloalkylene, or a group        —CH₂CH(OZ′)CH₂—(OCH₂—CH(OZ′)CH₂)₂— wherein Z′ is hydrogen,        C₁-C₁₈alkyl, allyl, benzyl, C₂-C₁₂alkanoyl or benzoyl.

(k′) A compound of the formula (1k)

wherein G, G₁₁ are as defined above.

(I′) A compound of the formula (11)

wherein G, G₁₁ are as defined above.

(m′) A compound of the formula (1m)

wherein G is as defined above, n₈ is 1, 2 or 3,

-   -   if n₈ is 1, G₅₁ is -G₅₀—O—CO-G₅₆; G₅₂ is —O—CO-G₅₆; and G₅₃ is        hydrogen; where G₅₆ is alkyl or —NH-alkyl of 1 to 18 carbon        atoms or —NH-cycloalkyl of 5 to 8 carbon atoms;    -   if n₈ is 2, G₅₁ is alkylene of 1 to 18 carbon atoms,        hydroxyalkylene of 3 to 18 carbon atoms, cycloalkylene of 5 to 8        carbon atoms, cycloalkenylene or hydroxycycloalkylene of 5to 8        carbon atoms, alkenylene of 3 to 18 carbon atoms, or a straight        or branched chain alkylene of 1 to 4 carbon atoms or        hydroxyalkylene of 2 to 4 carbon atoms substituted by phenyl or        by phenyl substituted by one or two alkyl of 1 to 4 carbon        atoms; or G₅₁ is a divalent acyl radical of an aliphatic,        cycloaliphatic, araliphatic or aromatic dicarboxylic acid or of        a dicarbamic acid, preferably an acyl radical of an aliphatic        dicarboxylic acid having 2-18 C atoms, of a cycloaliphatic or        aromatic dicarboxylic acid having 8-14 C atoms,    -   if n₈ is 3, G₅₁ is alkanetriyl of 1 to 18 carbon atoms,        hydroxyalkanetriyl of 3 to 18 carbon atoms, cycloalkanetriyl of        5 to 8 carbon atoms, cycloalkenetriyl of 5 to 8 carbon atoms,        alkenetriyl of 3 to 18 carbon atoms, a straight or branched        chain alkanetriyl of 1 to 4 carbon atoms substituted by phenyl        or by phenyl substituted by one or two alkyl of 1 to 4 carbon        atoms;    -   if n₈ is 2or 3,    -   G₅₂ is —O-G₁₂; —N(G₁₃)G₁₄; —O-G₁₅; —COO-T₇; or is a group of one        of the formulae        and    -   G₅₃ is hydrogen or, if G₅₂ is —OG₁₅, is O-G′₁₅;    -   or G₅₂ and G₅₃ together are ═O; or a group of the formula        where G₁₁ and G₁₂ are as defined above under (a′) if n₁ is 1;        G₁₃ and G₁₄ are as defined above under (b′) if n₂ is 1; G₁₅ and        G′₁₅ are as defined above under (c′) if n₃ is 1; G₁₈, G₁₉, A, E,        D^(IV), x₁ are as defined above under (e′); T₇ is as defined        above under (j′) if n₇ is 1;    -   G₅₄ is as defined for G₁₂ under (a′) if n₁ is 2; G₅₅ is as        defined for G₁₄ under (b′) if n₂ is 2; G₅₆ is as defined for T₇        under (j′) if n₇ is 2.

Of special technical importance is a sterically hindered amine lightstabilizer of the hydroxyhydrocarbyloxyamine class, wherein E₁ ispreferably C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl or C₇-C₁₅aralkyl each of whichis substituted in the aliphatic part by 1-3 OH groups, especially 1 OHgroup.

Thus, present invention also pertains to a flame retardant compositionstabilized against deleterious effects of light and weatheringcomprising

-   -   a) a polyolefin, and    -   b) a flame retardant selected from        -   b1) melamin based flame retardants and/or ammonium            polyphosphate,        -   b2) bis-(hexachlorocyclopentadieno) cyclooctane,        -   b3) tris-(2,3-dibromopropyl)-isocyanurate,        -   b4) ethylene-bis-tetrabromophthalimide; and    -   c) a sterically hindered amine light stabilizer of the        hydroxyhydrocarbyloxyamine class.

Further, the instant invention pertains to a process for imparting lightstability and flame retardancy to a thermoplastic polymer, which processcomprises adding to said polymer a combination of the flame retardanttris-(2,3-dibromopropyl)-isocyanurate and a sterically hindered aminelight stabilizer of the hydrocarbyloxyamine orhydroxyhydrocarbyloxyamine class. A flame retardant and light stabilizedcomposition comprising

-   -   a) a polyolefin,    -   b) tris-(2,3-dibromopropyl)-isocyanurate as a flame retardant        and    -   c) a sterically hindered amine light stabilizer of the        hydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class        is another preferred object of present invention.

Preferred components a and c and amounts thereof in the novel processand novel compositions are as described above.

Components b and c of the instant invention and optional furthercomponents may readily be incorporated into the polymer by conventionaltechniques, at any convenient stage prior to the manufacture of shapedarticles therefrom. For example, the additives may be mixed with thepolymer in dry powder form, or a suspension or emulsion of thestabilizer may be mixed with a solution, suspension, or emulsion of thepolymer. The additives may be added to component (a), individually ormixed with one another. If desired, the individual components can bemixed with one another in the melt (melt blending) before incorporationinto the material to be stabilized. Components b and/or c and optionalfurther additives may be incorporated, for example, before or aftermolding or also by applying the dissolved or dispersed stabilizermixture to the material to be stabilized, with or without subsequentevaporation of the solvent. The additives of component b and/or c aswell as further additives can also be added to the material to bestabilized in the form of a masterbatch which contains these componentsin a concentration of, for example, about 2.5% to about 25% by weight;in such operations, the polymer can be used in the form of powder,granules, solutions, suspensions or in the form of latices.

Incorporation can take place prior to or during the shaping operation,or by applying the dissolved or dispersed compound to the polymer, withor without subsequent evaporation of the solvent. In the case ofelastomers, these can also be stabilized as latices. A furtherpossibility for incorporating the stabilizers of the invention intopolymers is to add them before, during or directly after thepolymerization of the corresponding monomers. In the case of additionprior to or during the polymerization, the stabilizers of the inventioncan also act as a regulator of the chain length of the polymers (chainterminator).

Components b and c of the invention can judiciously be incorporated bythe following methods:

-   -   as emulsion or dispersion (e.g. to latices or emulsion        polymers),    -   as a dry mixture during the mixing in of additional components        or polymer mixtures,    -   by direct introduction into the processing apparatus (e.g.        extruders, internal mixers, etc),    -   as solution or melt.

The additive combination of present components b and c is useful formany applications, especially outdoor applications, including thefollowing:

Thermoplastic olefins (TPO), e.g. paintable thermoplastic olefins

Polypropylene molded articles

Polyethylene film

Molded polypropylene with brominated flame retardants

Molded thermoplastic olefin with brominated flame retardants

Polethylene film with brominated flame retardants

Thermoplastic elastomers with other costabilizers

Grease-filled wire and cable insulation

Coatings over plastic substrates

Polyolefin tanks or containers containing chemicals

Polyolefin films with an antifog agent

Polyolefin films with IR thermal fillers such as hydrotalcites, e.g.DHT4A

Polyolefin films with an antistatic agent

Flame-resistant molded polypropylene articles

Flame-resistant molded thermoplastic olefins

Flame-resistant polethylene film

Pre-formed films for lamination to plastic substrates

Electronic appliance

Containers, boxes, bins for storage and transportation

Automotive applications e.g. dashboard, back board

Furniture e.g. stadion seats, public seats

Roofing sheets

Roofing membranes

Flooring materials

Liners

Profiles, especially window and door profiles

Geomembranes.

The materials containing the stabilizers described herein can be usedfor the production of moldings, extruded articles, rotomolded articles,injection molded articles, blow molded articles, mono- and multilayerfilms, extruded profiles, surface coatings and the like.

The resulting stabilized compositions of the invention may optionallyalso contain various conventional additives, preferably in amounts from0.01 to 10%, more preferably from about 0.025 to about 2%, andespecially from about 0.1 to about 1% by weight of component (a), suchas the materials listed below, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctyl-thiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydrocuinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tertbutyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O—, N— and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tertbutyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyidiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers

2.1.2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300;

where R=3′-tert-butyl-4′-hydroxy-5′-2H-benxotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethyibenzyl)phenyl]benzotriazole.

2.2.2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Conventional sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)-malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,5-(2-ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone,1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)amino)-s-triazine,1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-on-4-yl)amino)-s-triazine,a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.(136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8.2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl) phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methyinitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecylnitrone,N-octadecyl-alpha-heptadecyinitrone,N-hexadecyl-alpha-heptadecyinitrone,N-ocatadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecyinitrone,N-octadecyl-alpha-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxyl-amine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

15. Amine oxides, for example amine oxide derivatives as disclosed inU.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide. U.S. Pat. Nos. 5,844,029 and 5,880,191 disclose the use ofsaturated hydrocarbon amine oxides towards the stabilization ofthermoplastic resins. It is disclosed that the thermoplasticcompositions may further contain a stabilizer or mixture of stabilizersselected from phenolic antioxidants, hindered amine light stabilizers,ultraviolet light absorbers, organic phosphorus compounds, alkalinemetal salts of fatty acids and thiosynergists. The co-use of amineoxides with other stabilizers towards stabilizing polyolefins is notexemplified.

Further preferred compositions comprise, in addition to components (b)and (c) further additives, in particular phenolic antioxidants, lightstabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 ofthe list), further sterically hindered amines (item 2.6 of the list),light stabilizers of the benzotriazole and/or o-hydroxyphenyltriazineclass (items 2.1 and 2.8 of the list), phosphites and phosphonites (item4 of the list) and peroxide-destroying compounds (item 5.) of the list.

Additional additives (stabilizers) which are also particularly preferredare benzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

The instant composition can additionally contain another UV absorberselected from the group consisting of the s-triazines, the oxanilides,the hydroxybenzophenones, benzoates and the α-cyanoacrylates.Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzo-triazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof. Preferred are additional componentsselected from pigments, dyes, plasticizers, antioxidants, thixotropicagents, levelling assistants, basic costabilizers, further lightstabilizers like UV absorbers and/or sterically hindered amines, metalpassivators, metal oxides, organophosphorus compounds, hydroxylamines,and mixtures thereof, especially pigments, phenolic antioxidants,calcium stearate, zinc stearate, UV absorbers of the2-(2′-hydroxyphenyl)benzotriazole and 2-(2-Hydroxyphenyl)-1,3,5-triazineclasses, and sterically hindered amines.

It is one of the findings of present invention that an especiallyimproved performance, both in light stability and flame retardancy, maybe obtained if the thermoplastic polymer contains, besides the flameretardant, a combination of a conventional sterically hindered amine ofhigh molecular weight with a low molecular weight sterically hinderedamine of the hydroxyhydrocarbyloxyamine class. Thus, present inventionalso pertains to a flame retardant composition stabilized againstdeleterious effects of light and weathering comprising

-   -   A) a thermoplastic polymer,    -   B) a flame retardant selected from ammonium polyphosphate,        halogenated and/or melamin based flame retardants, and    -   C) a combination of sterically hindered amine light stabilizers        comprising        -   C1) a low molecular weight sterically hindered amine of the            hydroxyhydrocarbyloxyamine class, and        -   C2) a conventional high molecular weight sterically hindered            amine.

Preferred polymers (A) in these compositions are as initially explained(a).

The halogenated flame retardants useful as component (B) in compositionsof present invention may be selected from organic aromatic halogenatedcompounds such as halogenated benzenes, biphenyls, phenols, ethers oresters thereof, bisphenols, diphenyloxides, aromatic carboxylic acids orpolyacids, anhydrides, amides or imides thereof; organic cycloaliphaticor polycycloaliphatic halogenated compounds; and organic aliphatichalogenated compounds such as halogenated paraffins, oligo- or polymers,alkylphosphates or alkylisocyanurates. These components are largelyknown in the art, see e.g. U.S. Pat. No. 4,579,906 (e.g. col. 3, lines30-41), U.S. Pat. No. 5,393,812; see also Plastics Additives Handbook,Ed. by H. Zweifel, 5^(th) Ed., Hanser Publ., Munich 2001, pp. 681-698.

The halogenated flame retardant may be, for example, a chlorinated orbrominated compound, e.g. selected from the following compounds:

-   -   Chloroalkyl phosphate esters (ANTIBLAZE® AB-100, Albright &        Wilson; FYROL® FR-2, Akzo Nobel),    -   polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.),    -   decabromodiphenyl oxide (DBDPO; SAYTEX® 102E),    -   tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370®, FMC        Corp.),    -   bis(2,3-dibromopropyl ether) of bisphenol A (PE68),    -   brominated epoxy resin,    -   ethylene-bis(tetrabromophthalimide) (SAYTEX® BT-93),    -   bis(hexachlorocyclopentadieno)cyclooctane (DECLORANE PLUS®),    -   chlorinated paraffins,    -   1,2-bis(tribromophenoxy)ethane (FF680),    -   tetrabromo-bisphenol A (SAYTEX® RB100),    -   ethylene bis-(dibromo-norbornanedicarboximide) (SAYTEX® BN-451),    -   bis-(hexachlorocyclopentadieno) cyclooctane,    -   tris-(2,3-dibromopropyl)-isocyanurate,    -   ethylene-bis-tetrabromophthalimide.

Preferred as component (B) are brominated flame retardants.

Most preferred flame retardants (B) in these compositions of theinvention are

-   -   B1) melamin based flame retardants and/or ammonium        polyphosphate,    -   B2) bis-(hexachlorocyclopentadieno) cyclooctane,    -   B3) tris-(2,3-dibromopropyl)-isocyanurate,    -   B4) ethylene-bis-tetrabromophthalimide,    -   B5) 1,2,5,6,9,10-hexabromo-cyclo-dodecan,    -   B6) ethane-1,2-bis(pentabromophenyl),    -   B7) tris(3-bromo-2,2-(bromomethyl)propyl) phosphate.

Especially preferred flame retardants (B) in these compositions of theinvention are as initially explained for component (b).

The flame retardant (B) is often contained in an amount from 0.5 to 50%by weight of the polymeric substrate (A); more preferred dosages for themost preferred flame retardants (B) are as initially explained forcomponent (b).

The ratio (B):(C) in these compositions is preferably in the range from20:1 to 250:1.

The ratio (C1):(C2) in these compositions is often in the range from 1:5to 5:1. In case that the polymeric substrate (A) is a polyolefin, thelow molecular weight component (C1) is preferably used in about the sameor in a larger amount than (C2), e.g. 40-95 parts by weight of (C1) on100 total parts by weight of component (C) consisting of (C1) and (C2).

In a polyolefin with main component polyethylene, the low molecularweight part (C1) often will amount about half of the total amount ofcomponent (C), e.g. from 40 to about 70, more specifically from 45 toabout 55% by weight of total component (C).

In a polyolefin with main component polypropylene, the low molecularweight part (C1) often will amount rather more than half of the totalamount of component (C), e.g. from 50 to about 90, more specificallyfrom 60 to about 85% by weight of total component (C).

Under such conditions in a polyolefin, the low molecular weightcomponent (C1) may also be of the hydrocarbyloxyamine class. Thus,another object of the invention pertains to a composition comprising

-   -   A) a polyolefin,    -   B) a flame retardant selected from ammonium polyphosphate,        halogenated and/or melamin based flame retardants, and    -   C) a combination of sterically hindered amine light stabilizers        comprising, on 100 parts by weight of total component (C),        -   C1) 40 to 95 parts by weight a low molecular weight            sterically hindered amine of the hydrocarbyloxyamine class,            and        -   C2) 5 to 60 parts by weight of a conventional high molecular            weight sterically hindered amine.

The low molecular weight sterically hindered amine of thehydroxyhydrocarbyloxyamine or, where appropriate, hydrocarbyloxyamineclass (C1) usually is from the molecular weight range 200 to 1000 g/mol,especially 300 to 800 g/mol. It may be one compound or a mixture ofcompounds, each fulfilling the molecular weight condition. Especiallypreferred are, for example,

-   -   1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;    -   bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;    -   bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate;    -   1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.

The high molecular weight sterically hindered amine (C2) is of theconventional type containing 2,2,6,6-tetramethyl-4-piperidyl moietieswhose nitrogen atoms are unsubstituted (secondary sterically hinderedamine) or substituted by alkyl, especially methyl (alkylated tertiarysterically hindered amine) or are part of a polymeric backbone(polymeric tertiary sterically hindered amine). It usually is from themolecular weight range 1200 to 10000 g/mol, especially 1500 to 5000g/mol. Examples for such compounds useful in the composition of theinvention can be found among those listed under item 2.6 above, e.g. thefollowing compounds:Examples for Secondary Sterically Hindered Amines of High MolecularWeight

where n is mainly from the range 3-5.Examples for Methylated Tertiary Sterically Hindered Amines of HighMolecular Weight

Example for Polymeric Tertiary Sterically Hindered Amine of HighMolecular Weight

Especially preferred compounds of component (C2) are those containing2,2,6,6-tetramethyl-4-piperidyl moieties whose nitrogen atoms areunsubstituted or alkyl, especially methyl substituted. Especiallypreferred compounds of component (C2) are also containing triazinemoieties as structural backbones.

In general, component (C) is contained in an amount from 0.01 to 10%,preferably from 0.05 to 5% by weight, especially from 0.1 to 3% byweight, based on the polymer component (A). The weight ratio (C1):(C2)preferably ranges from 1:10 to 10:1; most preferably from 1:1 to 10:1.

Further components optionally to be used in these compositions of theinvention, and methods of using them, are as initially explained.

The following examples are for illustrative purposes only and are not tobe construed to limit the instant invention in any manner whatsoever.Room temperature depicts a temperature in the range 20-25° C.Percentages are by weight unless otherwise indicated.

Abbreviations:

-   -   v parts by volume    -   w parts by weight    -   ¹Hnmr nuclear magnetic resonance (NMR) of ¹H    -   m/z mass spectrometry (atomic units)    -   amu molecular weight in g/mol (=atomic units)    -   M_(n) number average of molecular weight (usually determined by        GPC)    -   PP polypropylene    -   PE polyethylene

PE-LD low density polyethylene (LDPE)

Sterically hindered amines of the hydrocarbyloxyamine orhydroxyhydrocarbyloxyamine class (present component c) for use in theexamples are the compounds

Further stabilizers used in the examples are compounds of formulae

Compounds c2, c3 and A-G are commercial stabilizers available from CibaSpecialty Chemicals.

Example 1

Sample preparation: Polymer powder and stabilizers are pre-mixed(Henschel mixer, 800 rpm, room temperature), pigment powder and flameretardant are added as concentrate in PP and homogenized in a drummixer. Further homogenization and granulation is achieved by extrusion(Collin® twin screw extruder, max 200° C., 100 rpm). Subsequently, themixture is processed into a flat film by means of a single screwextruder (max 200° C., 70 rpm) equipped with a corresponding nozzle(sample dimension 2 mm thickness, 10 cm width).

Weathering: Punched samples are exposed to accelerated weathering(Atlas® WOM Ci 65, 0.35 W/m² (at 340 nm), 102 min dry, 18 min waterspray, 63° C. black panel temperature. The effect of weathering on thesurface is assessed in the following manner: Visual inspection ofchalking (chalking indicates decomposition on the surface).

Gloss: Minolta; degradation of surface reduces the reflection ofpolarized light (60° gloss as

-   -   defined in DIN 67530).    -   ΔE: Colour change (according to DIN 6174).        Formulation:

84 parts by weight of polypropylene-ethylene copolymer (Novolen® PPG1022),

15 parts by weight of a PE-based flame retardant masterbatch containing51% by weight of ethylene-bis-tetrabromophthalimide (b4) and 17% byweight of Sb₂O₃,

1 part by weight of TiO₂ and

0.2 parts by weight of blue pigment (Cromophtal blue 4GNP) andstabilizers as shown in the following table (amounts given in % byweight of the total formulation).

The results are shown in the following table. TABLE Surface assessmentafter weathering for 2000 h Exp. # Stabilizers Visual Gloss Δ E a* nonechalking 3 5.9 b 0.3% c1 unchanged 53 1.5 0.1% B 0.2% F c* 0.3% Cchalking 8 4.6 0.1% B 0.2% F d 0.3% c1 unchanged 51 2.8 0.1% B 0.2% E e*0.3% C chalking 8 5.9 0.1% B 0.2% E*comparative example

Samples containing the combination of flame retardant and stericallyhindered amine of present invention show no chalking, better gloss anddistinctly less colour change than samples wherein present component chas been replaced by another sterically hindered amine.

Example 2

Samples are prepared and subjected to accelerated weathering asdescribed in example 1.

Formulation:

89 parts by weight of polypropylene-ethylene copolymer (Novolen® PPG1022),

10 parts by weight of a PE based flame retardant masterbatch containing30% by weight of

tris-(2,3-dibromopropyl)-isocyanurate (b3) and 15% Sb₂O₃,

1 part by weight of TiO₂ and

0.2 parts by weight of blue pigment (Cromophtal blue 4GNP) andstabilizers as shown in the following table (amounts given in % byweight of the total formulation). The results are shown in the followingtable. TABLE Surface assessment after weathering for 2000 h Exp. #Stabilizers Visual Gloss Δ E a* none chalking 8 7.5 b 0.3% c1 unchanged58 1.7 0.1% B 0.2% F c* 0.3% C chalking 12 6.4 0.1% B 0.2% F d 0.3% c3unchanged 57 3 0.1% B 0.2% E e 0.3% c1 unchanged 63 2.3 0.1% B 0.2% E f*0.3% C chalking 14 7.1 0.1% B 0.2% E*comparative example

Replacing compound c3 in the above example by the same amount of c2 orc4 also leads to superior properties.

Example 3

Sample preparation: Polymer powder, flame retardant and stabilizers arepre-mixed (Henschel mixer, 800 rpm, roopm temperature), pigment is addedas concentrate in PE-LD and homogenized in a drum mixer. Furtherhomogenization and granulation is achieved by extrusion (Berstorff® twinscrew extruder (max 220° C., 100 rpm). Test samples (44×68×2 mm) areobtained by compression moulding (Engel) at a plastification temperatureof max 200° C. and a forming temperature of 50° C. Acceleratedweathering and assessment of the samples is done as described in example1.

Formulation:

73 parts by weight of polypropylene-ethylene copolymer (Appryl® 3060),

25 parts by weight of melamin polyphosphate (flame retardant b1,Melapur® P 46),

2 parts by weight of blue pigment masterbatch (10% Cromophtal blue 4GNPin PE-LD)

0.15 parts by weight of a commercial phenolic antioxidant (1:1 mixtureof tris(2,4-di-t-butylphenyl)phosphite and pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], available fromCiba Specialty Chemicals)

and stabilizers as shown in the following table (amounts given in % byweight of the total formulation). The results are shown in the followingtable. TABLE Surface assessment after weathering for 1000 h Exp. #Stabilizers Visual Gloss Δ E a* 0.2% A chalking 5 23.9 0.2% D b 0.133% Aunchanged 19 3.9 0.266% c1*comparative example

Example 4

Sample preparation, accelerated weathering and assessment of the samplesis done as described in example 3.

Formulation:

82 parts by weight of polypropylene-ethylene copolymer (Appryl® 3060),

12 parts by weight of bis-(hexachlorocyclopentadieno) cyclooctane (flameretardant b2, Dechloran Plus®),

4 parts by weight of Sb₂O₃

2 parts by weight of blue pigment masterbatch (10% Cromophtal blue 4GNPin PE-LD)

0.15 parts by weight of a commercial phenolic antioxidant (1:1 mixtureof tris(2,4-di-t-butylphenyl)phosphite and pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], available fromCiba Specialty Chemicals)

and stabilizers as shown in the following table (amounts given in % byweight of the total formulation). The results are shown in the followingtable. TABLE Surface assessment after weathering for 1000 h Exp. #Stabilizers Visual Gloss Δ E a* 0.2% B chalking 7 5.1 0.2% C b 0.2% Aunchanged 35 0.7 0.2% c1*comparative example

Example 5

Sample preparation, accelerated weathering and assessment of the samplesis done as described in example 3. Formulation is identical with the oneof example 3 except that the melamin polyphosphate flame retardant isreplaced by the same amount of ammonium polyphosphate (flame retardantb1; Exolith® AP 752). Results are shown in the following table. TABLESurface assessment after weathering for 1500 h Exp. # Stabilizers VisualGloss Δ E a* 0.2% A chalking 5 21.4 0.2% D b 0.2% A unchanged 28 3.10.2% c1*comparative example

Example 6

Sample preparation, accelerated weathering and assessment of the samplesis done as described in example 3.

Formulation:

92 parts by weight of polypropylene-ethylene copolymer (Appryl® 3060),

4 parts by weight of tris(3-bromo-2,2-(bromomethyl)propyl) phosphat(flame retardant, FR 372 from Dead See Bromine),

2 parts by weight of Sb₂O₃

2 parts by weight of blue pigment masterbatch (10% Cromophtal blue 4GNPin PE-LD)

0.15 parts by weight of a commercial phenolic antioxidant (1:1 mixtureof tris(2,4-di-t-butylphenyl)phosphite and pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], available fromCiba Specialty Chemicals)

and stabilizers as shown in the following table (amounts given in % byweight of the total formulation). The results are shown in the followingtable. TABLE Surface assessment after weathering for 1500 h Exp. #Stabilizers Visual Gloss Δ E a* 0.2% B chalking 6 7.6 0.2% C b 0.2% Aunchalking 56 0.4 0.2% c1 c 0.4% c1 unchalking 56 0.3*comparative example

Example 7

Sample preparation, accelerated weathering and assessment of the samplesis done as described in example 3.

Formulation:

88 parts by weight of polypropylene-ethylene copolymer (Appryl ® 3060),

8 parts by weight of ethane-1,2-bis(pentabromophenyl) (flame retardantb6, Saytex® 8010 ),

4 parts by weight of Sb₂O₃

2 parts by weight of blue pigment masterbatch (10% Cromophtal blue 4GNPin PE-LD)

0.15 parts by weight of a commercial phenolic antioxidant (1:1 mixtureof tris(2,4-di-t-butylphenyl)phosphite and pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], available fromCiba Specialty Chemicals)

and stabilizers as shown in the following table (amounts given in % byweight of the total formulation). The results are shown in the followingtable. TABLE Surface assessment after weathering for 750 h Exp. #Stabilizers Visual Gloss Δ E a* 0.2% B Chalking 10 6.5 0.2% C 0.1% G b0.13% A Unchanged 38 5.3 0.27% c1 0.1% G*comparative example

1. A process for imparting weathering stability, light stability andflame retardancy to a thermoplastic polymer (a) by addition of a flameretardant (b) and a sterically hindered amine (c), which process ischaracterized in that the flame retardant (b) is selected from the groupconsisting of b1) melamine based flame retardants and/or ammoniumpolyphosphate, b2) bis-(hexachlorocyclopentadieno) cyclooctane, b3)tris-(2,3-dibromopropyl)-isocyanurate, b4)ethylene-bis-tetrabromophthalimide, b5)1,2,5,6,9,10-hexabromo-cyclo-dodecane and b6)]1,2-bis(pentabromophenyl)ethane; and the sterically hindered amine (c)is selected from the group consisting o hydrocarbyloxyamine and of thehydroxyhydrocarbyloxyamine sterically hindered amine light stabilizers.provided that the flame retardant is not (b4) if the sterically hinderedamine is hydroxyhydrocarbyloxyamines.
 2. Process of claim 1 forimparting outdoor weathering stability and flame retardancy to athermoplastic polymer, which is a polyolefin.
 3. Process of claim 1wherein the sterically hindered amine light stabilizer of component (c)is a cyclic sterically hindered amine conforming to the formula

wherein G₁ and G₂ are independently alkyl of 1 to 4 carbon atoms or aretogether pentamethylene, and E₁ is C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl orC₇-C₁₅aralkyl; or E₁ is C₁-C₁₈alkyl, C₅-C₁₂cyclo-alkyl or C₇-C₁₅aralkyleach of which is substituted in the aliphatic part by 1-3 OH groups; Tis a divalent organic radical required to complete formula (I) to form,together with the hindered amine nitrogen atom and the two quaternarycarbon atoms substituted by G₁ and G₂, a five- or six-membered aliphaticring structure; or component (c) is an oligomeric or polymeric hinderedamine molecule made from the reaction of a dialkyl ester or isocyanatewith a compound of the formula (I) wherein E₁ contains 1 OH group and Tis —CH₂—CH(OH)—CH₂—; or component (c) is a simple diester or urethanederivative of a compound of the formula (I) wherein E₁ contains 1 OHgroup and T is —CH₂—CH(OH)—CH₂—.
 4. Process of claim 1, whereincomponent (c) is added in an amount of 0.01 to 10% by weight, based onthe weight of the polymer (a).
 5. Process of claim 1, wherein componentb1) is added in an amount from 1 to 50% by weight, or one or more ofcomponents b2), b3), b4), b5), b6) in a total amount from 0.5 to 20% byweight, each amount based on the weight of the polymer (a).
 6. Processof claim 1 for imparting both weathering stability and flame retardancyto a polyethylene, polypropylene, or copolymer or blend thereof. 7.Process of claim 1 wherein one or more further components selected fromthe group consisting of pigments, dyes, plasticizers, antioxidants,thixotropic agents, levelling assistants, basic costabilizers, furtherlight stabilizers, metal passivators, metal oxides, organophosphoruscompounds, hydroxylamines, and mixtures thereof, are also added. 8.Process of claim 7, wherein the further component is selected from thegroup consisting of pigments, phenolic antioxidants, calcium stearate,zinc stearate, sterically hindered amines and UV absorbers.
 9. Processof claim 8, wherein the further component is selected from the groupconsisting of the 2-(2′-hydroxyphenyl)benzotriazole,2-(2-hydroxyphenyl)-1,3,5-triazine and the 2-hydroxyphenylbenzophenoneUV absorbers.
 10. (canceled)
 11. A flame retardant and light stabilizedcomposition comprising (a) a polyolefin, and b) a flame retardantselected from the group consisting of b1) melamine based flameretardants and/or ammonium polyphosphate, b2)bis-(hexachlorocyclopentadieno) cyclooctane, b3)tris-(2,3-dibromopropyl)-isocyanurate, b5)1,2,5,6,9,10-hexabromo-cyclo-dodecane and b6)1,2-bis(pentabromophenyl)ethane; and c) a hydroxyhydrocarbyloxyaminesterically hindered amine light stabilizer.
 12. A flame retardant andlight stabilized composition according to claim 11 wherein thesterically hindered amine light stabilizer of component (c) a compoundof the formula

wherein G₁ and G₂ are independently alkyl of 1 to 4 carbon atoms or aretogether pentamethylene, and E₁ is C₁-C₁8alkyl, C₅-C₁₂cycloalkyl orC₇-C₁₅aralkyl each of which is substituted in the aliphatic part by 1-3OH groups; T is a divalent organic radical required to complete formula(I) to form, together with the hindered amine nitrogen atom and the twoquaternary carbon atoms substituted by G₁ and G₂, a five- orsix-membered aliphatic ring structure; or component (c) is an oligomericor polymeric hindered amine molecule made from the reaction of a dialkylester or isocyanate with a compound of the formula (I) wherein E₁contains 1 OH group and T is —CH₂—CH(OH)—CH₂—; or component (c) is asimple diester or urethane derivative of a compound of the formula (I)wherein E₁ contains 1 OH group and T is —CH₂—CH(OH)—CH₂—.
 13. A flameretardant and light stabilized composition according to claim 11 whereincomponent (c)1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.14-18. (canceled)
 19. Composition according to claim 11 containingcomponent (b) in an amount from 0.5 to 50% by weight, and component (c)in an amount of 0.01 to 10% by weight, each based on the weight ofcomponent (a).
 20. Composition according to claim 11 additionallycontaining one or more further components selected from the groupconsisting of pigments, dyes, plasticizers, antioxidants, thixotropicagents, levelling assistants, basic costabilizers, metal passivators,metal oxides, organophosphorus compounds, hydroxylamines, further lightstabilizers and mixtures thereof.
 21. Composition according to claim 11additionally containing one or more further components selected from thegroup consisting of pigments, phenolic antioxidants, calcium stearate,zinc stearate, sterically hindered amines and 2-hydroxy-benzophenone,2-(2′-hydroxyphenyl)-1,3,5-triazine UV absorbers.
 22. Molded or extrudedarticle comprising a composition according to claim 11.